Hexamethylenetetramine adducts with haloacetic acid esters

ABSTRACT

New compositions are made by the 1:1 molar reaction of hexamethylenetetramine with a haloacetic acid ester. The quaternary salts thus formed are colorless crystalline solids, readily soluble in water and having biological activity. They are bactericides which also have fungicidal activity.

United States Patent Chester E. Pawloski Bay City, Mich.

Mar. 5, 1970 Nov. 30, 1971 The Dow Chemical Company Midland, Mich.

[72] Inventor [2i Appl. No. [22] Filed [45] Patented [73] Assignee [54] HEXAMETHYLENETETRAMINE ADDUCTS WITH HALOACETIC ACID ESTERS 9 Claims, No Drawings [52] US. Cl 260/248.5, 424/249 [5 l] Int. Cl C07d 55/14 [50] Field ofSearch 260/2485 [56] References Cited UNITED STATES PATENTS 3,524,854 8/1970 Kuhn Primary Examiner-John M. Ford Attorneys-Griswold and Burdick and C. E. Rehberg HEXAMETHYLENETETRAMINE ADDUCTS WITH HALOACETIC ACID ESTERS BACKGROUND OF THE INVENTION Hexamethylenetetramine is known to form quaternary salt adducts with certain halohydrocarbons (Wolf and Scott, US. Pat. No. 3,228,829). These adducts show bactericidal and other biological activity.

SUMMARY OF THE INVENTION New, biologically active quaternary salts are made by the reaction of hexamethylenetetramine (hereinafter, HMTA) with haloacetic acid esters in a l:l molar ratio. These salts are colorless, water-soluble, stable, crystalline compounds having high activity as bactericides as well as other biological activity. These compounds have the formula COOR wherein X is Br or I and R is lower alkyl, alkenyl, haloalkenyl or alkynyl containing up to four carbon atoms.

The above compounds are conveniently made by contacting HMTA and the appropriate haloacetic acid ester in a suitable inert solvent. The products are insoluble in most common organic solvents; hence, they precipitate from such solvents as they are formed. Suitable such solvents include the halohydrocarbons such as methylene chloride, chloroform, perchloroethylene and the like.

SPECIFIC EMBODlMENTS OF THE INVENTION A. Preparation of Compounds, General Procedure Essentially equimolar amounts of HMTA and haloacetic acid ester dissolved in chloroform, about l.52.5 l. of the latter being used per g. mole of HMTA. The solutions were stirred at or slightly above room temperature for 3-6 hr., though the reaction appeared to be complete in less time. The products precipitated as colorless crystals as the reaction proceeded. The addition of acetone sometimes favored complete precipitation. The crystals were separated by filtration and dried in vacuum. No attempt was made to recover product or unused reactant from the filtrate. Results are tabulated below.

i TABLE] HMTA Salts of Formula I (X==Br) Example R 1: Yield M.P.. C.

1 Methyl 93 15M d) 2 Ethyl 8: I51

3 Z-Propynyl 89 l49-50(d) 4 LBromeallyl 89 l50-52( d 5 Allyl 57 158(6)) 6 Z-Chloroallyl 88 l53-54(d) In addition to those shown in the above table, other similar salts that can be made in the same way and that have generally similar properties and uses include those wherein R is n-butyl, isobutyl, methallyl, 2,3-dichloroallyl, and the salts corresponding to those above wherein X is l.

The compounds of the invention have powerful biological activity. They are of es cial interest as bactericides.

Thus, the compoun s of examples l, 2, 4, 5 and 6, when incoon CH, /CH:

Cgs /CH: X

H: CH: HI

wherein X is Br or I and R is an alkyl, alkenyl, haloalkenyl or alkynyl group of up to four carbon atoms.

2. The compound of claim 1 wherein X is Br.

3. The compound of claim I wherein X is l.

4. The compound of claim 1 wherein R is alkyl.

5. The compound of claim 1 wherein R is alkenyl.

6. The compound of claim 1 wherein R is bromoalkenyl.

7. The compound of claim 1 wherein R is chloroalkenyl.

8. The compound of claim 1 wherein R is alkynyl.

9. The compound of claim 2 wherein R is methyl, ethyl, allyl, 2-bromoallyl, 2-chloroallyl or propynyl.

* i i I Q 

2. The compound of claim 1 wherein X is Br.
 3. The compound of claim 1 wherein X is I.
 4. The compound of claim 1 wherein R is alkyl.
 5. The compound of claim 1 wherein R is alkenyl.
 6. The compound of claim 1 wherein R is bromoalkenyl.
 7. The compound of claim 1 wherein R is chloroalkenyl.
 8. The compound of claim 1 wherein R is alkynyl.
 9. The compound of claim 2 wherein R is methyl, ethyl, allyl, 2-bromoallyl, 2-chloroallyl or propynyl. 